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Aqueous emulsion polymerization of fluorinated monomers in the presence of a partially fluorinated oligomer as an emulsifier

A technology for fluorinating monomers and oligomers, used in chemical/physical processes, chemical instruments and methods, transportation and packaging, etc.

Inactive Publication Date: 2008-06-04
3M INNOVATIVE PROPERTIES CO
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Suspension polymerization usually does not involve the use of surfactants, but produces significantly larger polymer particles than in the case of aqueous emulsion polymerization

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0120] Embodiment 1 (preparation has the VDF-HFP oligomer of ion terminal group)

[0121] Into a polymerization kettle equipped with an impeller agitator system and having a total capacity of 47.5 L was added 22.0 L of deionized water. The anaerobic kettle was then heated to 90°C and the stirrer system was set to 240 rpm. Add 202g dimethyl ether (Me 2 O), 200 g of hexafluoropropylene (HFP) to an absolute pressure of 25 bar and 85 g of vinylidene fluoride (VDF) were added to a reaction pressure of 4.0 bar absolute. Polymerization was initiated by adding 130 mL of a 31% aqueous solution of ammonium peroxodisulfate (APS). When the reaction started, the reaction temperature was maintained and the absolute reaction pressure was kept at 4.0 bar by feeding VDF and HFP into the gas phase at a feed ratio (HFP(kg) / VDF(kg)) of 0.653. In addition, an aqueous solution of ammonium peroxodisulfate (APS) having a concentration of 31% was continuously fed into the reactor at a feed rate of ...

Embodiment 2

[0130] Embodiment 2 (utilize the oligomer among the embodiment 1 to carry out the polymerization of TFE / HFP / VDF)

[0131] To a 50 L polymerization vessel was added 24 L of deionized water containing 5 L of the emulsifier solution prepared in Example 1. Air was removed by alternating operations of evacuation and pressurization to 4 bar with nitrogen. The vessel was then pressurized with HFP at 8.6 bar, VDF at 1.9 bar and TFE at 4.2 bar. The temperature in the vessel was adjusted to 70°C. 200 mL of an aqueous solution containing 9 g of ammonium persulfate (APS) was added to the vessel. The stirring speed was 240 rpm. Polymerization temperature and pressure were kept constant by feeding TFE, HFP and VDF in a constant ratio of 1:0.412:0.488. When 0.8 kg of TFE was consumed, the polymerization was stopped by stopping the monomer feed and reducing the stirring speed. The container was emptied, and the resulting dispersion was discharged. The dispersion thus obtained had a soli...

Embodiment 3

[0133] Example 3 (polymerization using oligomers prepared in situ)

[0134] 28 L of deionized water was added to the 50 L polymerization vessel. Air was removed by alternating operations of evacuation and pressurization to 4 bar with nitrogen. The vessel was then pressurized with HFP at 5.0 bar, VDF at 3.5 bar and ethane at 0.8 bar. The temperature of the vessel was adjusted to 70°C. Add 200mL aqueous solution to the container, wherein the aqueous solution contains 12g APS, 22mg CuSO 4 ·5H 2 O and 150 g of 10% aqueous sodium hydroxide solution. By pumping into a vessel containing 3 g of Na dissolved in 100 mL of deionized 2 S 2 o 5 aqueous solution to initiate the reaction. The stirring speed was 240 rpm. The temperature was kept constant and no monomer was added. When the reaction pressure was reduced by 1.5 bar, about 100 g of oligomers were formed. Polymerization was then initiated by pressurizing the vessel with 8.5 bar TFE to produce a fluorocopolymer of TFE, H...

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Abstract

The present invention relates to a method for making a fluoropolymer comprising an aqueous emulsion polymerization of one or more fluorinated monomers wherein said aqueous emulsion polymerization is carried out in the presence of an oligomer that comprises one or more ionic groups, has a partially fluorinated backbone, a number average molecular weight of not more than 2000 g / mol and that has a combination of repeating units different from that of the fluoropolymer that is being produced by the polymerization of said one or more fluorinated monomers. Since the polymerization of the one or more fluorinated monomers to produce the desired fluoropolymer is carried out in the presence of the oligomer, the resulting dispersion will contain the oligomer in addition to the fluoropolymer. Thus, in a further aspect, the invention relates to an aqueous dispersion of a fluoropolymer comprising the oligomer.

Description

[0001] Cross References to Related Patent Applications [0002] This patent application claims priority from British Patent Application No. GB0511779.1 filed 10 June 2005, which is hereby incorporated by reference in its entirety. technical field [0003] The present invention relates to aqueous emulsion polymerization of fluorinated monomers to prepare fluoropolymers. Background technique [0004] Fluoropolymers (i.e., polymers with a fluorinated backbone) have been known for a long time and have been favored due to several desirable properties such as heat resistance, chemical resistance, weather resistance, UV stability, etc. for various applications. A variety of fluoropolymers are described, for example, in "Modern Fluoropolymers", edited by John Scheirs (published by Wiley Science Publishing Company, 1997). Well-known or commercial fluoropolymers include: polytetrafluoroethylene (PTFE), copolymers of tetrafluoroethylene (TFE) and hexafluoropropylene (HFP) (FEP polyme...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F14/18C08L27/12C08F6/20C08F6/22C08L27/18C09K23/52
CPCC08F6/22C08L27/12C08F6/20C08L27/18C08F14/18C08L2205/02C08F2/22C08L2666/04
Inventor 克劳斯·欣策米夏埃尔·于尔根斯哈拉尔德·卡斯帕凯·赫尔穆特·洛哈斯安德烈亚斯·R·毛雷尔蒂尔曼·齐普莱斯
Owner 3M INNOVATIVE PROPERTIES CO